1. Field of the Invention
The present invention relates to a gas barrier film and, more specifically, it relates to a laminate type gas barrier film suitable to substrates for various kinds of devices and coating films for the devices. Further, the invention also relates to an organic electroluminescence device excellent in durability and flexibility obtained by using the gas barrier film (referred to hereinafter as an EL device).
2. Description of the Related Art
Gas barrier films in which thin films of metal oxide such as aluminum oxide, magnesium oxide, and silicon oxides are formed on the surfaces of plastic substrates or films have been generally used so far for packaging of articles requiring shielding of steams or various gases such as oxygen, or packaging application for preventing denaturation of foodstuffs, industrial products, and medicines. Further, the gas barrier films have also been started for use in substrates of liquid crystal display devices, solar cells, electroluminescence (EL) devices or the like in addition to the packaging use. Particularly, in transparent substrates which have been applied progressively to liquid crystal display devices, EL devices, etc., high level of demands such as long time reliability, high degree of freedom in view of shape, and capability of display on a curved surface have been required in addition to the demand for reduction in the weight and increase in the size.
Recently, in the field of the liquid crystal display devices, the EL devices, etc., film substrates such as made of transparent plastics have been started for use instead of glass substrates, which are heavy, tended to be cracked and difficult in increasing the area. Further, since the film substrates such as made of transparent plastics not only can cope with the requirements described above but also can be applied to the roll-to-roll system, they are advantageous over glass materials in view of the productivity and the reduction of cost. However, film substrates such as of transparent plastics involve a problem of poor gas barrier property in comparison with glass. Since steam or air permeates in a case of a substrate of poor gas barrier property, when it is used for example to a liquid crystal display device, liquid crystals in a liquid crystal cell are deteriorated and deteriorated portions result in display defects to deteriorate the display quality,
For solving such problems, it has been known to form a thin film of a metal oxide on the film substrate described above, and use the gas barrier film as a transparent substrate. As gas barrier films used for packaging materials and liquid crystal display devices, those formed by vapor depositing silicon oxide on a plastic film (for example, in JP-B No. 53-12953 (p1 to p3) and those formed by vapor depositing aluminum oxide (for example, in JP-A No. 58-217344 (p1 to p4) are known and they have a steam barrier property of about 1 g/m2/day. However, the steam barrier property as low as about 0.1 g/m2/day has been demanded recently for the film substrate along with increase in the size of liquid crystal displays or development for highly fine displays.
Further, most recently, development has been progressed, for example, in organic EL displays or highly fine color liquid crystal displays requiring further higher barrier property and it has been demanded for a substrate having a performance of higher barrier property, particularly, a steam barrier property of less than 0.1 g/m2/day while maintaining transparency usable therein.
For coping with such a demand, film deposition by way of a sputtering method or a CVD method of forming a thin film using plasmas generated by glow discharge under low pressure conditions has been studied as means capable of expecting highly barrier performance. Further, it has been attempted to obtain desired performance by lamination structure (for example, in JP-A No. 2003-206361 (p2-p3)).
As a thin film material of excellent barrier property, silicon nitride and silicon oxynitride have also been utilized and lamination of them has also been attempted (for example, in JP-A No. 2003-206361 (p2-p3)).
However, in a case of using the film substrate, since restriction is imposed on the substrate temperature during film formation, a barrier layer of a sufficiently dense structure can not be formed, and a film having a barrier property enough to satisfy the requirement has not yet been manufactured.
On the other hand, it has been proposed a technique of preparing a barrier film having an alternate laminate structure of organic layer/inorganic layer by a vacuum vapor deposition method (for example, refer to U.S. Pat. No. 6,413,645B1 (p4, [2-54] to p8, [8-22])) and “Thin Solid films” written by Affinito, et al., (1996), p. 290 to p291 (p63 to p67)), a film having a barrier property required for the organic EL film substrate has been obtained.
However, in a case of continuously forming the films for the organic layer and the inorganic layer, it gives rise to a problem such as contamination between both of the process, and it is necessary to form a multi-layered structure of at least six or more layers in order to provide a barrier film of high reliability for use in organic EL devices. Since it has been difficult to make the performance and the high throughput compatible, it has been demanded for developing a new film forming system suitable to continuous film forming process.